Increasing security needs require compact and portable detection tools for the rapid and reliable identification of explosives used in improvised explosive devices (IEDs). We report of an easy-to-use optical sensor for both vapour-phase and solution-phase identification of explosive mixtures that uses a cross-reactive fluorimetric sensor array comprising chemically responsive fluorimetric indicators composed of aromatic aldehydes and polyethyleneimine. Ammonium nitrate-nitromethane (ANNM) was analyzed by paper microzone arrays and nanofiber sensor mats. Progress toward wearable sensors based on electrospun nanofiber mats is outlined.